EP0335158B1 - Stickstoffhaltige polymere Verbindungen - Google Patents
Stickstoffhaltige polymere Verbindungen Download PDFInfo
- Publication number
- EP0335158B1 EP0335158B1 EP89104344A EP89104344A EP0335158B1 EP 0335158 B1 EP0335158 B1 EP 0335158B1 EP 89104344 A EP89104344 A EP 89104344A EP 89104344 A EP89104344 A EP 89104344A EP 0335158 B1 EP0335158 B1 EP 0335158B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- epoxypropyl
- alkyl
- mol
- polyamines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0246—Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/0253—Polyamines containing sulfur in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
- C08G73/022—Preparatory process from polyamines and epihalohydrins
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
Definitions
- the present invention relates to nitrogen-containing, crosslinkable polymeric compounds, their preparation and their use as auxiliaries in papermaking.
- water-soluble, curable resins are obtained by reacting epichlorohydrin with ammonia and / or polyamines.
- the object of the present invention was to produce water-soluble, storage-stable compounds which can be crosslinked in the neutral or alkaline pH range and which contain no or only very small amounts of organically bound halogen. A gradual or complete replacement of epihalohydrin or dihalohydrin should be achieved by using suitable halogen-free crosslinkers.
- the task was also to achieve wet strengths on paper that correspond to the commercially available polyamine-epihalohydrin resins.
- the compounds A1), A2) and A3) are preferred.
- the preferred molar ratio of the amines A 3 ⁇ ) to dicarboxylic acids A3 ⁇ ) is 0.8 to 1.4: 1.
- R16 are C1-C9-alkyl, cyclohexyl or optionally substituted by C1-C4-alkyl, C1-C5-alkoxy or hydroxy-substituted phenyl or benzyl.
- the polyamide amines Depending on the molar ratio A3 ⁇ : A3 ⁇ , the polyamide amines contain amino or carboxyl end groups.
- the polymers contain amide structures corresponding to diamines II.
- the crosslinkable compounds have a solids content of 5 to 30% by weight, preferably 10 to 25% by weight, a viscosity of 10 to 600 mPa.s, preferably 15 to 500 mPa.s at 25 ° C. Their molecular weight is approximately 1500 to 250,000, preferably 2000 to 200,000. (Weight average)
- reaction products according to the invention are preferably produced in an aqueous medium.
- polar solvents such as methanol, ethanol, isopropanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, dimethylformamide, ethyl acetate or preferably their mixtures with water can also be used.
- the reaction of the starting components A and B is carried out by treating the aqueous or aqueous-organic about 10 to 60% solutions or emulsions of the two components at a temperature of 20 to 95 ° C, preferably 40 to 85 ° C, until one Sample of the reaction mixture in the form of a 15% aqueous or aqueous-organic solution or emulsion at 25 ° C has a viscosity of 15 to 300 mPa.s, preferably 20 to 200 mPa.s.
- Acids are then added to the mixture, which becomes more viscous, in order to end the action and to stabilize the self-crosslinking products, so that the pH is between 1 and 6, preferably 1.5 and 5.5.
- Acid derivatives include acid-reacting derivatives of the abovementioned acids, in particular anhydrides and acid salts, such as e.g. Alkali hydrogen sulfates to understand.
- the solids content of the products is then adjusted to the desired content by dilution with water and / or solvent.
- Diethylene triamine triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, dipropylenetriamine, methyl bis (3-aminopropyl) amine, dihexamethylene triamine or mixtures thereof or mixtures thereof with 50 mol% of a diamine of the formula (II), preferably ethylenediamine.
- Preferred dicarboxylic acids (A3 ⁇ ) are:
- Preferred compound (A3 ⁇ ) is ⁇ -caprolactam.
- Aminocarboxylic acids such as those in lactams or their lactams, as described, for example, in German Offenlegungsschrift 2 925 567.
- Preferred 1,2-alkyleneimine (A5) is ethyleneimine.
- Preferred examples of 2,3-epoxypropyl sulfonates or 2-hydroxypropyl-1,3-bissulfonic acid esters (B) are:
- the paper is equipped with the polymers according to the invention in a manner known per se at pH values from 5 to 9.
- the crosslinkable compounds are preferably added in bulk in the form of aqueous solutions or emulsions to the aqueous suspension of the paper stock; this is then processed into paper.
- the amounts added are between 0.4 and 4.0% by weight of the solution or emulsion (based on paper raw material) with a respective polymer content (active ingredient content) of 10 to 20% by weight. If the requirements for wet strength are particularly high, even higher amounts are used. For example, in laminate papers with a high ash content and low basis weight, additional amounts of 6.0% by weight and more are required.
- 61.0 g 2 are added dropwise at 30 ° C. in 20 minutes to a template from 120 g of a 50% aqueous solution of a polyamide amine from DE-B 1 771 043, column 4, lines 4 to 25 and 350 ml of water , 3-epoxypropyl methanesulfonate and stirred for 30 minutes at 35 ° C.
- the mixture is then heated to 70 ° C. and 450 ml of water and 15.0 g of methyl bis (3-aminopropyl) amine are added as the viscosity increases. After the desired viscosity has been reached, the mixture is acidified to pH 2.8 using a sulfuric acid solution and the solids content is adjusted as desired. Solids content: 15.0% by weight Viscosity: 28 mPa.s (25 ° C) organ. Cl content: 0.001% by weight organ. S content: 1.5% by weight
- the mixture is then stirred at 30 ° C. for 30 minutes and then heated to 70 ° C.
- the mixture is acidified to pH 3.0 using a sulfuric acid solution and the solids content of the stable emulsion is adjusted as desired.
- Solids content 14.1% by weight
- Viscosity 465 mPas / 25 ° C organ.
- Cl content ⁇ 0.01% by weight
- Bleached pine sulphite pulp is ground in the Dutch at a consistency of 2.5% to a freeness of 38 ° Schopper-Riegler. 100 g of this are placed in a beaker and diluted to 1 l with water.
- test strips 1.5 cm wide are cut out of each sheet of paper and immersed in distilled water for 5 minutes.
- the wet strips are then clamped in a tensile testing machine and the wet breaking load is determined.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Polyamides (AREA)
- Epoxy Resins (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3810424 | 1988-03-26 | ||
DE3810424A DE3810424A1 (de) | 1988-03-26 | 1988-03-26 | Stickstoffhaltige polymere verbindungen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0335158A1 EP0335158A1 (de) | 1989-10-04 |
EP0335158B1 true EP0335158B1 (de) | 1994-07-06 |
Family
ID=6350844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89104344A Expired - Lifetime EP0335158B1 (de) | 1988-03-26 | 1989-03-11 | Stickstoffhaltige polymere Verbindungen |
Country Status (6)
Country | Link |
---|---|
US (2) | US5082527A (fi) |
EP (1) | EP0335158B1 (fi) |
JP (1) | JPH028219A (fi) |
AT (1) | ATE108192T1 (fi) |
DE (2) | DE3810424A1 (fi) |
FI (1) | FI891397A (fi) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5364927A (en) * | 1990-08-24 | 1994-11-15 | Henkel Corporation | Wet strength resin composition and method of making same |
US5239047A (en) * | 1990-08-24 | 1993-08-24 | Henkel Corporation | Wet strength resin composition and method of making same |
US5189142A (en) * | 1990-08-24 | 1993-02-23 | Henkel Corporation | Wet strength resin composition and method of making same |
DE4101822A1 (de) * | 1991-01-23 | 1992-07-30 | Bayer Ag | Pigmentdruck auf faserstoffen |
FI933763A (fi) * | 1992-08-29 | 1994-03-01 | Hoechst Ag | Graensytaktiva foereningar baserade pao alkoxylerade fettaminer |
US7576162B2 (en) * | 2005-06-30 | 2009-08-18 | Akzo Nobel N.V. | Chemical process |
WO2011009811A1 (en) | 2009-07-20 | 2011-01-27 | Akzo Nobel Coatings International B.V. | Adhesive system and method of producing a wood based product |
WO2011009812A1 (en) | 2009-07-20 | 2011-01-27 | Akzo Nobel Coatings International B.V. | Adhesive system and method of producing a wood based product |
EP2649145B1 (en) | 2010-12-10 | 2014-11-26 | Akzo Nobel Coatings International B.V. | Aqueous adhesive composition comprising a synthetic polymer and lupin protein |
MX2014001530A (es) | 2011-08-25 | 2014-02-27 | Ashland Licensing & Intellectu | Metodo para aumentar las ventajas de la fuerza ayuda en la produccion de papel y carton. |
US11332889B2 (en) | 2019-05-03 | 2022-05-17 | First Quality Tissue, Llc | Absorbent structures with high absorbency and low basis weight |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3361590A (en) * | 1962-07-25 | 1968-01-02 | Monsanto Co | Polyglycidylpolyamine treated polysaccharides |
DE1595302A1 (de) * | 1966-02-08 | 1970-03-05 | Basf Ag | Verfahren zur Herstellung von wasserloeslichen Kondensationsprodukten |
DE1771814C2 (de) * | 1968-07-16 | 1974-05-09 | Bayer Ag, 5090 Leverkusen | Hilfsmittel-Verwendung für die Papierfabrikation |
GB8429273D0 (en) * | 1984-11-20 | 1984-12-27 | Dow Chemical Nederland | Producing nitrogen containing prepolymer |
DE3609984A1 (de) * | 1986-03-25 | 1987-10-01 | Bayer Ag | Verfahren zur behandlung von fasermaterialien |
DE3708544A1 (de) * | 1987-03-17 | 1988-09-29 | Bayer Ag | Stickstoffhaltige, wasserloesliche verbindungen |
DE3810425A1 (de) * | 1988-03-26 | 1989-10-12 | Bayer Ag | Stickstoffhaltige, wasserloesliche, polymere verbindungen |
-
1988
- 1988-03-26 DE DE3810424A patent/DE3810424A1/de not_active Withdrawn
-
1989
- 1989-03-11 EP EP89104344A patent/EP0335158B1/de not_active Expired - Lifetime
- 1989-03-11 DE DE58907991T patent/DE58907991D1/de not_active Expired - Fee Related
- 1989-03-11 AT AT89104344T patent/ATE108192T1/de active
- 1989-03-14 US US07/323,457 patent/US5082527A/en not_active Expired - Fee Related
- 1989-03-23 JP JP1069404A patent/JPH028219A/ja active Pending
- 1989-03-23 FI FI891397A patent/FI891397A/fi not_active Application Discontinuation
-
1991
- 1991-08-14 US US07/745,043 patent/US5093470A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
FI891397A (fi) | 1989-09-27 |
DE3810424A1 (de) | 1989-10-12 |
US5093470A (en) | 1992-03-03 |
EP0335158A1 (de) | 1989-10-04 |
ATE108192T1 (de) | 1994-07-15 |
FI891397A0 (fi) | 1989-03-23 |
DE58907991D1 (de) | 1994-08-11 |
US5082527A (en) | 1992-01-21 |
JPH028219A (ja) | 1990-01-11 |
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